The present invention relates to organometallic compounds of transition metals with an indenyl ligand bound in the 2-position and substituted in the 1,3-position, a process for their production, and their use as catalysts for the (co)polymerization of olefinic and/or diolefinic monomers.
Corresponding to the IUPAC nomenclature the positions of the ring atoms of indene are identified as follows in the present application: 
The production of substituted indenes [Spaleck, W.; Rohrmann, J.; Antberg, M.; EP-A1-0 530 647] is known in the relevant literature, and substituted indenes may be produced for example starting from 1-indanones [Smonou, I.; Ofranopopuolos, M. Synth. Commun. 1990, 20 (9), 1387].
The synthesis of 2-bromoindenes is based on known processes for their production [Billups, W.; J. Org. Chem. 1980, 23, 4638; Porter, H. D.; Suter, C. M. J. Am. Chem. Soc. 1935, 57, 2022; Koelsch, C. J. Org. Chem. 1960, 25, 130; Weixcex2, R.; Luft, S.; Monatsh. Chem. 1927, 48, 341].
Stereorigid chiral metallocenes with bridged indenyl ligands are known as catalysts for the production of polyolefins. In this connection, it has been found that the nature and position of the substituents on the indenyl anion and the nature and position of the bridge have an influence on both the catalyst activity and also the polymer properties. Many of the indenyl metallocenes have a bridge in the 1-position (1-indenyl metallocenes).
The bis(1-indenyl)-metallocenes substituted in the 2- and/or 4-position with indenyl residues bridged in the 1-position are particularly important for the production of highly isotactic polypropylene with a high degree of crystallinity and a high melting point. (EP-A1-485 821, EP-A1-485 823, EP-A2-519237). Also important are the bis(1-indenyl)-metallocenes benzanellated in the 4,5-position (see Organometallics 1994, 13, 964-970).
It is also known to use organometallic compounds with only one indenyl anion as catalysts (constrained geometry complexes with 1-indenyl ligands, see U.S. Pat. No. 5,026,798, WO-97/15583-A1).
Organometallic compounds of transition metals that contain an indenyl ligand and a cyclopentadienyl ligand are known from WO-94/11406-A1, the indenyl ligand being substituted in the 2-position; this substituent may also be formed as a bridge to the second ligand. The examples of implementation illustrate multistage productions with extremely unsatisfactory yields that lead in the case of bridged compounds to 1-cyclopentadenyl-2-(2-indenyl)-ethane zirconium chloride, to bis-(2-indenyl)-methane zirconium dichloride, or to dimethyl-bis-(2-indenyl)-silane zirconium dichloride, which still contains impurities. A multistage synthesis pathway to ethylene-bis-(2-indenyl) titanium dichloride is described in Organometallics 1993, 12, 5012-5015. On account of the multistage synthesis and the numerous purification operations the achievable yield is very low. On account of the synthesis pathway the structural multiplicity is restricted to ethylene-bridged ligands.
Ethylene-bridged bis(2-indenyl) zirconocenes are disclosed in EP-A2-941 997. These zirconocenes are used for the production of special polyolefins with low molecular weights.
Silyl-bridged 2-indenyl metallocenes and a process for the production of organometallic compounds with an indenyl ligand bonded in the 2-position are described in EP-A1-0 940 408.
Moreover, a process for the production of amorphous polypropylenes using a catalyst system based on monocyclopentadienyl transition metal complexes is described in U.S. Pat. No. 5,504,169. The cyclopentadienyl ring bonded to the transition metal complex is substituted symmetrically with no, two or four substituents.
Transition metal complexes with 1,3-disubstituted indenyl ligands bridged in the 2-position are not known.
It has now been shown that such organometallic catalysts whose bridging attaches at least one 1,3-disubstituted indenyl anion to the 2-position have special properties as polymerization catalysts; they produce in fact predominantly atactic polymers with high molecular weights in the (co)polymerization of xcex1-olefins. It was, therefore, desirable to find a production process for such catalysts bridged in the 2-position by at least one 1,3-disubstituted indenyl anion.
A further object of the invention was to provide a catalyst that is suitable for the synthesis of high molecular weight EPDM.
The present invention relates to a process for the production of organometallic compounds of transition metals with 2-indenyl ligands substituted in the 1,3-position that correspond to the general formula (I), 
wherein
A denotes the benzo system or the tetrahydrocyclohexyl system,
Q1, Q2 are identical or different and, as substituent of the 2-indenyl system substituted in the 1,3-position, denote hydrogen, C1-C4-alkyl, C6-C14-aryl, C7-C10-aralkyl, C1-C4-alkoxy, C1-C4-alkylthio, phenoxy, phenylthio, di-C1-C4-alkylamino, C6-C14-aryl-C1-C4-alkylamino, di-C6-C14-arylamino, dibenzylamino, tri-C1-C4-alkylsilyl, di-C1-C4-alkylboranyl, phenyl-C1-C4-alkylboranyl, diphenylboranyl, di-C1-C4-alkylphosphoryl, diphenylphosphoryl or phenyl-C1-C4-alkylphosphoryl,
Q3 are identical or different and, as substituent of the 2-indenyl system substituted in the 4,5,6,7-position, denote hydrogen, C1-C4-alkyl, C6-C14-aryl, C7-C10-aralkyl, C1-C4-alkoxy, C1-C4-alkylthio, phenoxy, phenylthio, di-C1-C4-alkylamino, C6-C14-aryl-C1-C4-alkylamino, di-C6-C14-arylamino, dibenzylamino, tri-C1-C4-alkylsilyl, di-C1-C4-alkylboranyl, phenyl-C1-C4-alkylboranyl, diphenylboranyl, di-C1-C4-alkylphosphoryl, diphenylphosphoryl or phenyl-C1-C4-alkylphosphoryl,
M1 is a transition metal from Group IV, V or VI of the Periodic System of the Elements according to IUPAC 1985,
X denotes an anion,
n is a number from zero to 4 that is determined by the valency and the bonding state of M1,
m is a number from zero to 4 that is determined by the number of the radicals Q3,
Y is a bridge from the group of xe2x80x94C(R1R2)xe2x80x94, xe2x80x94Si(R1R2)xe2x80x94, xe2x80x94Ge(R1R2)xe2x80x94, xe2x80x94C(R1R2)xe2x80x94C(R3R4)xe2x80x94, xe2x80x94C(R1R2)xe2x80x94Si(R3R4)xe2x80x94 or xe2x80x94Si(R1R2)xe2x80x94, wherein R1, R2, R3 and R4 independently of one another denote hydrogen, halogen, straight-chain or branched C1-C10-alkyl, C5-C8-cycloalkyl, C6-C14-aryl or C7-C10-aralkyl, and
Z is a second ligand from the group of open-chain and cyclic, optionally anionic xcfx80-systems, xe2x80x94N(R5)xe2x80x94, xe2x80x94P(R6)xe2x80x94, |N(R5R7)xe2x80x94, |P(R6R8)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, |OR5xe2x80x94 or |SR5xe2x80x94, wherein the vertical line to the left of the element symbol N, P, O and S denotes an electron pair, and the bonding between Z and M1 is ionic, covalent or co-ordinative, and wherein R5, R6, R7 and R8 independently of one another have the same range of meanings as R1 to R4, and R5 and R7 may in addition denote xe2x80x94Si(R1R2R3), and R6 and R8 may in addition denote xe2x80x94Si(R1R2R3), xe2x80x94OR1, xe2x80x94SR1 or xe2x80x94N(R1R2),
characterized in that a halogenated indene substituted in the 1,3-position of the formula (II) 
in which Hal1 denotes Cl, Br or I and Q1, Q2 and Q3 and m have the above meanings,
is reacted with an elementary metal selected from Groups I, II or XII of the Periodic System according to IUPAC 1985 or a corresponding metal compound in an amount in the range from 1 to 100 moles of elementary metal/metal compound per mole of (II) and with a dihalide of the bridge Y of the formula
Hal2xe2x80x94Yxe2x80x94Hal3xe2x80x83xe2x80x83(III),
in which
Hal2 and Hal3 independently of one another denote Cl, Br or I and
Y has the above range of meanings,
in an amount of 1 to 20 moles of (III) per mole of (II), wherein in the case where Y has the meaning xe2x80x94Si(R1R2)xe2x80x94, xe2x80x94Ge(R1R2)xe2x80x94 or xe2x80x94Si(R1R2)xe2x80x94Si(R3R4)xe2x80x94, the reaction of (II) with (i) elementary metal/metal compound, and of (ii) with (III) may also take place simultaneously, and the reaction product of the formula 
wherein Q1, Q2, Q3, Y and Hal3 have the above meanings,
is reacted, optionally after it has been separated, with a Z derivative of the formula
ZM2pxe2x80x83xe2x80x83(Va)
or
ZR9pxe2x80x83xe2x80x83(Vb),
in which
M2 denotes Li, Na, K or xe2x80x94MgHal4, wherein Hal4 has the range of meanings of Hal2,
p represents the number 1 or 2,
R9 denotes hydrogen, xe2x80x94Si(R1R2R3) or Sn(R1R2R3), and
Z, R1, R2 and R3 have the above meanings,
with the release of a compound of the formula
M2Hal3xe2x80x83xe2x80x83(VIa)
or
R9Hal3xe2x80x83xe2x80x83(VIb),
in which M2, R9 and Hal3 have the above meanings,
optionally in the presence of an auxiliary base to form the 2-indenyl compound of the formula 
in which Q1, Q2, Q3, Y, Z and m have the above meanings and which may be present as a dianion, and in which Z may furthermore carry M2, R9 or an electron pair,
and is then reacted further with a transition metal compound of the formula
M1Xqxe2x80x83xe2x80x83(VIII),
in which
M1 and X have the above meanings and
q is a number from 2 to 6 that is determined by the oxidation state of M1.